This is a 371 of PCT EP 97/05317, filed Sep. 29, 1997.
The invention relates to novel substituted 2,4-diamino-1,3,5-triazines, to processes and to novel intermediates for their preparation and to their use as herbicides.
A number of substituted 2,4-diamino-triazines is already known from the (patent) literature (cf U.S. Pat. No. 3,816,419, U.S. Pat. No. 3,932,167, EP 191496, EP 273328, EP 411153/WO 90/09378, JP 62294669xe2x80x94cited in Chem. Abstracts 109: 129062v). However, these compounds have hitherto not attained any particular importance.
This invention, accordingly, provides the novel substituted 2,4-diamino-1,3,5-triazines of the general formula (I) 
in which
R1 represents hydrogen or optionally hydroxyl-, cyano-, halogen- or C1-C4-alkoxy-substituted alkyl having 1 to 6 carbon atoms,
R2 represents hydrogen, represents formyl, represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkylcarbonyl, alkoxycarbonyl or alkylsulphonyl having in each case 1 to 6 carbon atoms in the alkyl groups, or represents in each case optionally cyano-, halogen-, C1-C4-alkyl-, halogeno-C1-C4-alkyl-, C1-C4-alkoxy, halogeno-C1-C4-alkoxy- or C1-C4-alkoxy-carbonyl-substituted phenylcarbonyl, naphthylcarbonyl, phenylsulphonyl or napththylsulphonyl,
R3 represents optionally cyano-, halogen- or C1-4-alkoxy-substituted alkyl having 1 to 6 carbon atoms or represents optionally cyano-, halogen- or C1-C4-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms,
X represents a substituent from the following group:
hydroxyl, cyano, nitro, halogen, in each case optionally hydroxyl-, cyano- or halogen-substituted alkyl or alkoxy having in each case 1 to 6 carbon atoms, in each case optionally halogen-substituted alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms in the alkyl groups, in each case optionally hydroxyl-, cyano-, nitro-, halogen-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy- or C1-C4-halogenoalkoxy-substituted phenyl or phenoxy, and
Z represents hydrogen, hydroxyl, halogen, represents in each case optionally hydroxyl-, cyano-, nitro-, halogen-, C1-C4-alkoxy-, C1-C4-alkyl-carbonyl-, C1-C4-alkoxy-carbonyl-, C1-C4-alkylthio-, C1-C4-alkylsulphinyl- or C1-C4-alkylsulphonyl-substituted alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms in the alkyl groups, represents in each case optionally halogen-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, or represents optionally cyano-, halogen- or C1-C4-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms,
but excluding the compounds
2-amino- 4-methoxy-6-[1-(3-chlorophenyl)-ethylamino]-1,3,5-triazine, 2-amino-4-methoxy-6-[1-(3-methyl-phenyl)-ethylamino]-1,3,5-triazine, 2-amino-4-chloro-6-[1-(3-trifluoromethyl-phenyl)-ethylamino]-1,3,5-triazine, 2-amino-4-chloro-6-[1-(3-nitrophenyl)-ethylamino-1,3,5-triazine, 2-amino-4-chloro-6-[1-(3-chloro-phenyl)-ethylamino]-1,3,5-triazine and 2-amino-4-chloro-6-[1-(3-methyl-phenyl)-ethylamino]-1,3,5-triazine
(which are already known from JP 62294669).
The novel 2,4-diamino-1,3,5-triazines of the general formula (I) are obtained when
(a) substituted biguanides of the general formula (II), 
xe2x80x83in which
R1, R2, R3 and X are each as defined above
and/or acid adducts of compounds of the general formula (II)
are reacted with alkoxycarbonyl compounds of the general formula (III)
Zxe2x80x94COxe2x80x94ORxe2x80x2xe2x80x83xe2x80x83(III)
xe2x80x83in which
Z is as defined above and
Rxe2x80x2 represents alkyl,
if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,
or when
(b) substituted aminotriazines of the general formula (IV) 
xe2x80x83in which
R3, X and Z are each as defined above and
X1 represents halogen or alkoxy
are reacted with nitrogen compounds of the general formula (V) 
xe2x80x83in which
R1 and R2 are each as defined above,
if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,
or when
(c) substituted aminotriazines of the general formula (VI), 
xe2x80x83in which
R1, R2 and Z are each as defined above and
X2 represents halogen or alkoxy
are reacted with amino compounds of the general formula (VII), 
xe2x80x83in which
R3 and X are each as defined above,
if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,
or when
(d) to prepare compounds of the formula (I), except for those where R2=H, 2,4-diamino-1,3,5-triazines of the general formula (Ia) 
xe2x80x83in which
R1, R3, X and Z are each as defined above
are reacted with alkylating, acylating or sulphonylating agents of the general formula (VIII)
Yxe2x80x94R2xe2x80x83xe2x80x83(VIII)
xe2x80x83in which
R2 is as defined abovexe2x80x94except for hydrogenxe2x80x94and
Y represents halogen, alkoxy, alkoxysulphonyloxy or acyloxy,
if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,
and, if appropriate, further conversions within the scope of the above definition of substituents are carried out by customary methods on the compounds of the general formula (I) obtained by the processes described under (a), (b), (c) or (d).
The novel substituted 2,4-diamino-1,3,5-triazines of the general formula (I) have strong and selective herbicidal activity.
The compounds of the general formula (I) according to the invention contain at least one asymmetrically substituted carbon atom and can therefore be present in different enantiomeric (R- and S-configured forms) or diastereomeric forms. The invention relates both to the different possible individual enantiomeric or stereoisomeric forms of the compounds of the general formula (I), and to the mixtures of these isomeric compounds.
In the definitions, the hydrocarbon chains, such as alkylxe2x80x94also in combination with heteroatoms, such as in alkoxy or alkylthioxe2x80x94are in each case straight-chain or branched.
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably represents fluorine, chlorine or bromine, and in particular represents fluorine or chlorine.
The invention preferably provides compounds of the formula (I) in which
R1 represents hydrogen or represents optionally hydroxyl-, cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted alkyl having 1 to 4 carbon atoms,
R2 represents hydrogen, represents formyl, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted alkyl, alkylcarbonyl, alkoxycarbonyl or alkylsulphonyl having in each case 1 to 4 carbon atoms in the alkyl groups, or represents in each case optionally cyano-, fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, n-, i-, s- or t-butoxy-, difluoromethoxy-, trifluoromethoxy-, methoxycarbonyl- or ethoxycarbonyl-substituted phenylcarbonyl or phenylsulphonyl,
R3 represents optionally hydroxyl-, cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted alkyl having 1 to 4 carbon atoms or represents optionally cyano-, fluorine-, chlorine-, methyl- or ethyl-substituted cycloalkyl having 3 to 6 carbon atoms,
x represents a substituent from the group below:
hydroxyl, cyano, nitro, fluorine, chlorine, bromine, iodine, in each case optionally hydroxyl-, cyano-, fluorine- or chlorine-substituted alkyl or alkoxy having in each case 1 to 4 carbon atoms, in each case optionally fluorine- or chlorine-substituted alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 4 carbon atoms in the alkyl groups, in each case optionally hydroxyl-, cyano-, nitro-, fluorine-, chlorine-, bromine-, iodine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, n-, i-, s- or t-butoxy-, difluoromethoxy- or trifluoromethoxy-substituted phenyl or phenoxy, and
Z represents hydrogen, hydroxyl, fluorine, chlorine, bromine, represents in each case optionally hydroxyl-, cyano-, nitro-, fluorine-, chlorine-, methoxy-, ethoxy-, acetyl-, propionyl-, methoxycarbonyl-, ethoxycarbonyl-, methylthio-, ethylthio-, methylsulphinyl-, ethylsulphinyl-, methylsulphonyl- or ethylsulphonyl-substituted alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 4 carbon atoms in the alkyl groups, represents in each case optionally fluorine-, chlorine- or bromine-substituted alkenyl or alkinyl having in each case 2 to 4 carbon atoms, or represents optionally cyano-, fluorine-, chlorine-, methyl- or ethyl-substituted cycloalkyl having 3 to 6 carbon atoms,
but excluding the compounds
2-amino-4-methoxy-6-[1-(3-chlorophenyl)-ethylamino]-1,3,5-triazine, 2-amino-4-methoxy-6-[1-(3-methyl-phenyl)-ethylamino]-1,3,5-triazine, 2-amino-4-chloro-6-[1-(3-trifluoromethyl-phenyl)-ethylamino]-1,3,5-triazine, 2-amino-4-chloro-6-[1-(3-nitrophenyl)-ethylamino]-1,3,5-triazine, 2-amino-4-chloro-6-[1-(3-chloro-phenyl)-ethylamino]-1,3,5-triazine and 2-amino-4-chloro-6-[1-(3-methyl-phenyl)-ethylamino]-1,3,5-triazine
(which are already known from JP 62294669).
The invention in particular relates to compounds of the formula (I) in which
R1 represents hydrogen or represents optionally hydroxyl-, cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl,
R2 represents hydrogen, represents formyl, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylsulphonyl or ethylsulphonyl, or represents in each case optionally cyano-, fluorine-, chlorine-, methyl-, ethyl-, trifluoromethyl-, methoxy-, ethoxy-, difluoromethoxy-, trifluoromethoxy-, methoxycarbonyl- or ethoxycarbonyl-substituted phenylcarbonyl or phenylsulphonyl,
R3 represents in each case optionally hydroxyl-, cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, or represents in each case optionally cyano-, fluorine-, chlorine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,
X represents a substituent from the group below:
hydroxyl, cyano, nitro, fluorine, chlorine, bromine, in each case optionally hydroxyl-, cyano-, fluorine- or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, in each case optionally fluorine- or chlorine-substituted acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl, in each case optionally hydroxyl-, cyano-, nitro-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy or trifluoromethoxy-substituted phenyl or phenoxy, and
Z represents hydrogen, hydroxyl, fluorine, chlorine, bromine, represents in each case optionally hydroxyl-, cyano-, nitro-, fluorine-, chlorine-, methoxy-, ethoxy-, acetyl-, propionyl-, methoxycarbonyl-, ethoxycarbonyl-, methylthio-, ethylthio-, methylsulphinyl-, ethylsulphinyl-, methylsulphonyl- or ethylsulphonyl-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, acetyl, propionyl, methoxycarbonyl,ethoxycarbonyl, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl, or represents in each case optionally fluorine-, chlorine- or bromine-substituted ethenyl, propenyl, butenyl, ethinyl, propinyl or butinyl,
but excluding the compounds
2-amino-4-methoxy-6-[1-(3-chlorophenyl)-ethylamino]-1,3,5-triazine, 2-amino-4-methoxy-6-[1-(3-methyl-phenyl)-ethylamino]-1,3,5-triazine, 2-amino-4-chloro-6-[1-(3-trifluoromethyl-phenyl)-ethylamino]-1,3,5-triazine, 2-amino-4-chloro-6-[1-(3-nitrophenyl)-ethylamino]-1,3,5-triazine, 2-amino-4-chloro-6-[1-(3-chloro-phenyl)-ethylamino]-1,3,5-triazine and 2-amino4-chloro-6-[1-(3-methyl-phenyl)-ethylamino]-1,3,5-triazine
(which are already known from JP 62294669).
The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and also, correspondingly, to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with each other at will, i.e. including combinations between the abovementioned preferred ranges.
Examples of the compounds of the formula (I) according to the invention are listed in the groups below. The general formulae here represent in each case the R enantiomers, the S enantiomers and the racemates.
Group 1 
Here, Z has, for example, the meanings given below:
Hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, chlorofluoromethyl, chlorobromomethyl, chlorodifluoromethyl, fluorodichloromethyl, bromodifluoromethyl, trichloromethyl, 1-fluoro-ethyl, 2-fluoro-ethyl, 1-chloro-ethyl, 2-chloro-ethyl, 1-chloro-1-fluoro-ethyl, 1-fluoro-propyl, 2-fluoro-propyl, 3-fluoro-propyl, 1-fluoro-1-methyl-ethyl, 2-fluoro-1-methyl-ethyl, 1-chloro-1-methyl-ethyl, 1-fluoro-1-methyl-propyl, 1-chloro-1-ethyl-propyl, 1-fluoro-1-ethyl-propyl, 1-chloro-1-ethyl-propyl, 1-fluoro-2-methyl-propyl, 1-chloro-2-methyl-propyl, 1-chloro-propyl, 2-chloro-propyl, 3-chloro-propyl, 1-chloro-1-methyl-ethyl, 2-chloro-1-methyl-ethyl, 1,1-difluoro-ethyl, 1,2-difluoro-ethyl, 1,1-dichloro-ethyl, 2,2,2-trifluoro-ethyl, 1,2,2,2-tetrafluoro-ethyl, perfluoroethyl, 1,1-difluoro-propyl, 1,1-dichloro-propyl, perfluoropropyl, 1-fluoro-butyl, 1-chloro-butyl, perfluoropentyl, perfluorohexyl, 1-hydroxyl-ethyl, acetyl, 1,1-bis-acetyl-methyl, 1-acetyl-1-methoxycarbonyl-methyl, 1-acetyl-1-ethoxycarbonyl-methyl, methoxymethyl, 1,1-dimethoxy-methyl, 1-methoxy-ethyl, 2-methoxy-ethyl, 1,1-dimethoxy-ethyl, ethoxymethyl, 1-ethoxyethyl, 2-ethoxyethyl, 2-methoxy-1-methyl-ethyl, 2-methoxy-1-ethyl-ethyl, 2-ethoxy-1-methyl-ethyl, 2-ethoxy-1-ethyl-ethyl, methylthiomethyl, ethylthiomethyl, 1-methylthio-ethyl, 2-methylthioethyl, 1-ethylthio-ethyl, 2-ethylthioethyl, methylsulphinylmethyl, ethylsulphinylmethyl, methylsulphonylmethyl, ethylsulphonylmethyl, methoxy, ethoxy, n- or i- propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, fluoromethoxy, difluoromethoxy, trifluoromethoxy, fluoroethoxy, difluoroethoxy, trifluoroethoxy, difluoromethylthio, trifluoromethylthio, vinyl, 1-chloro-vinyl, 2-chloro-vinyl, 1-fluoro-vinyl, 2-fluoro-vinyl, 1-bromo-vinyl, 2-bromo-vinyl, 1,2-dichloro-vinyl, 1,2-dibromo-vinyl, 1,2-difluoro-vinyl, 2,2-dichloro-vinyl, 2,2-difluoro-vinyl, 2,2-dibromo-vinyl, 1-chloro-2-fluoro-vinyl, 2-bromo-2-chloro-vinyl, trichlorovinyl, allyl, 2-chloro-allyl, 3-chloro-allyl, 3,3-dichloro-allyl, 1-propenyl, isopropenyl, 1-chloro-2-propenyl, 1-fluoro-2-propenyl, 1-bromo-2-propenyl, 1,2-dichloro-1-propenyl, 1,2-dibromo-1-propenyl, 1,2-difluoro-1-propenyl, 1,1-dichloro-2-propenyl, 1,1-dibromo-2-propenyl, 1,1-difluoro-2-propenyl, 1,1,3,3,3-pentafluoro-2-propenyl, 2-buten-1-yl, 2-buten-2-yl, 3-chloro-2-butenyl, 3-bromo-2-butenyl, 3,3,3-trifluoro-2-butenyl, ethinyl, 2-chloro-ethinyl, 2-bromo-ethinyl, 1-propinyl, 2-propinyl, 3,3,3-trifluoro-1-propinyl.
Group 2 
Here, Z has, for example, the meanings given above in group 1.
Group 3 
Here, Z has, for example, the meanings given above in group 1.
Group, 4 
Here, Z has, for example, the meanings given above in group 1.
Group 5 
Here, Z has, for example, the meanings given above in group 1.
Group 6 
Here, Z has, for example, the meanings given above in group 1.
Group 7 
Here, Z has, for example, the meanings given above in group 1.
Group 8 
Here, Z has, for example, the meanings given above in group 1.
Group 9 
Here, Z has, for example, the meanings given above in group 1.
Group 10 
Here, Z has, for example, the meanings given above in group 1.
Group 11 
Here, Z has, for example, the meanings given above in group 1.
Group 12 
Here, Z has, for example, the meanings given above in group 1.
Group 13 
Here, Z has, for example, the meanings given above in group 1.
Group 14 
Here, Z has, for example, the meanings given above in group 1.
Group 15 
Here, Z has, for example, the meanings given above in group 1.
Group 16 
Here, Z has, for example, the meanings given above in group 1.
Group 17 
Here Z has, for example, the meanings given above in group 1.
Group 18 
Here, Z has, for example, the meanings given above in group 1.
Group 19 
Here, Z has, for example, the meanings given above in group 1.
Group 20 
Here, Z has, for example, the meanings given above in group 1.
Group 21 
Here, Z has, for example, the meanings given above in group 1.
Group 22 
Here, Z has, for example, the meanings given above in group 1.
Group 23 
Here, Z has, for example, the meanings given above in group 1.
Group 24 
Here, Z has, for example, the meanings given above in group 1.
Group 25 
Here, Z has, for example, the meanings given above in group 1.
Group 26 
Here, Z has, for example, the meanings given above in group 1.
Group 27 
Here, Z has, for example, the meanings given above in group 1.
Group 28 
Here, Z has, for example, the meanings given above in group 1.
Group 29 
Here, Z has, for example, the meanings given above in group 1.
Group 30 
Here, Z has, for example, the meanings given above in group 1.
Group 31 
Here, Z has, for example, the meanings given above in group 1.
Group 32 
Here, Z has, for example, the meanings given above in group 1.
Group 33 
Here, Z has, for example, the meanings given above in group 1.
Group 34 
Here, Z has, for example, the meanings given above in group 1.
Group 35 
Here, Z has, for example, the meanings given above in group 1.
Group 36 
Here, Z has, for example, the meanings given above in group 1.
Group 37 
Here, Z has, for example, the meanings given above in group 1.
Group 38 
Here, Z has, for example, the meanings given above in group 1.
Group 39 
Here, Z has, for example, the meanings given above in group 1.
Group 40 
Here, Z has, for example, the meanings given above in group 1.
Group 41 
Here, Z has, for example, the meanings given above in group 1.
Group 42 
Here, Z has, for example, the meanings given above in group 1.
Group 43 
Here, Z has, for example, the meanings given above in group 1.
Group 44 
Here, Z has, for example, the meanings given above in group 1.
Group 45 
Here, Z has, for example, the meanings given above in group 1.
Group 46 
Here, Z has, for example, the meanings given above in group 1.
Group 47 
Here, Z has, for example, the meanings given above in group 1.
Group 48 
Here, Z has, for example, the meanings given above in group 1.
Group 49 
Here, Z has, for example, the meanings given above in group 1.
Group 50 
Here, Z has, for example, the meanings given above in group 1.
Group 51 
Here, Z has, for example, the meanings given above in group 1.
Group 52 
Here, Z has, for example, the meanings given above in group 1.
Group 53 
Here, Z has, for example, the meanings given above in group 1.
Group 54 
Here, Z has, for example, the meanings given above in group 1.
Group 55 
Here, Z has, for example, the meanings given above in group 1.
Group 56 
Here, Z has, for example, the meanings given above in group 1.
Group 57 
Here, Z has, for example, the meanings given above in group 1.
Group 58 
Here, Z has, for example, the meanings given above in group 1.
Group 59 
Here, Z has, for example, the meanings given above in group 1.
Group 60 
Here, Z has, for example, the meanings given above in group 1.
Group 61 
Here, Z has, for example, the meanings given above in group 1.
Group 62 
Here, Z has, for example, the meanings given above in group 1.
Group 63 
Here, Z has, for example, the meanings given above in group 1.
Group 64 
Here, Z has, for example, the meanings given above in group 1.
Group 65 
Here, Z has, for example, the meanings given above in group 1.
Group 66 
Here, Z has, for example, the meanings given above in group 1.
Using, for example, 1-[1-(4-chloro-phenyl)-ethyl]biguanide and methyl trifluoroacetate as starting materials, the course of the reaction in the process (a) according to the invention can be illustrated by the following equation: 
Using, for example, 2-chloro- 4[1-(3-fluoro-phenyl)-propylamino]-6-(1-chloro-ethyl)-1,3,5-triazine and ammonia as starting materials, the course of the reaction in the process (b) according to the invention can be illustrated by the following equation: 
Using, for example, 2-amino-4-methoxy-6-trifluoromethyl-1,3,5-triazine and 1-(4-ethyl-phenyl)-propylamine as starting materials, the course of the reaction in the process (c) according to the invention can be illustrated by the following equation: 
Using, for example, 2-amino- 4-(1-fluoro-1-methyl-ethyl)-6-[1-(2-methyl-phenyl)-ethylamino]-1,3,5-triazine and acetyl chloride as starting materials, the course of the reaction in the process (d) according to the invention can be illustrated by the following equation: 
The formula (II) provides a general definition of the substituted biguanides to be used as starting materials in the process (a) according to the invention for preparing compounds of the formula (I. In the formula (II), R1, R2, R3 and X each preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R1, R2, R3 and X.
Examples of the substituted biguanides of the formula (II)xe2x80x94where preference is in each case given to the racemates, the R enantiomers and the S enantiomersxe2x80x94which may be mentioned are:
1-(1-(2-fluoro-phenyl)-ethyl)-, 1-(1-(3-fluoro-phenyl)-ethyl)-, 1-(1-(4-fluoro-phenyl)-ethyl)-, 1-(1-(2-chloro-phenyl)-ethyl)-, 1-(1-(3-chloro-phenyl)-ethyl)-, 1-(1-(4-chloro-phenyl)-ethyl)-, 1-(1-(2-bromo-phenyl)-ethyl)-, 1-(1-(3-bromo-phenyl)-ethyl)-, 1-(1-(4-bromo-phenyl)-ethyl)-, 1-(1-(2-nitro-phenyl)-ethyl)-, 1-(1-(3-nitro-phenyl)-ethyl)-, 1-(1-(4-nitro-phenyl)-ethyl)-, 1-(1-(2-methyl-phenyl)-ethyl)-, 1-(1-(3-methyl-phenyl)-ethyl)-, 1-(1-(4-methyl-phenyl)-ethyl)-, 1-(1-(2-trifluoromethyl-phenyl)-ethyl)-, 1-(1-(3-trifluoromethyl-phenyl)-ethyl)-, 1-(1-(4-trifluoromethyl-phenyl)-ethyl)-, 1-(1-(2-methoxy-phenyl)-ethyl)-, 1-(1-(3-methoxy-phenyl)-ethyl)-, 1-(1-(4-methoxy-phenyl)-ethyl)-, 1-(1-(2-difluoromethoxy-phenyl)-ethyl)-, 1-(1-(2-difluoromethoxy-phenyl)-ethyl)-, 1-(1-(2-difluoromethoxy-phenyl)-ethyl)-, 1-(1-(2-trifluoromethoxy-phenyl)-ethyl)-, 1-(1-(3-trifluoromethoxy-phenyl)-ethyl)-, 1-(1-(4-trifluoromethoxy-phenyl)-ethyl)-, 1-(1-(2-methoxycarbonyl-phenyl)-ethyl)-, 1-(1-(2-ethoxycarbonyl-phenyl)-ethyl)-, 1-(1-(4-methoxycarbonyl-phenyl)-ethyl)-, 1-(1-(4-ethoxycarbonyl-phenyl)-ethyl)-, 1-(1-(2-methylthio-phenyl)-ethyl)-, 1-(1-(4-methylthio-phenyl)-ethyl)-, 1-(1-(2-methylsulphinyl-phenyl)-ethyl)-, 1-(1-(4-methylsulphinyl-phenyl)-ethyl)-, 1-(1-(2-methylsulphonyl-phenyl)-ethyl)- and 1-(1-(4-methylsulphonyl-phenyl)-ethyl)-biguanide.
Suitable acid adducts of compounds of the formula (II) are their addition products with protic acids, such as, for example with hydrogen chloride, hydrogen bromide, sulphuric acid, methanesulphonic acid, benzenesulphonic acid and p-toluenesulphonic acid.
The starting materials of the general formula (II), with the exception of 1-[1-(4-trifluoromethyl-phenyl)-ethyl]-biguanide (cf. U.S. Pat. No. 3,860,648), have hitherto not been disclosed in the literature; with the exception of 1-[1-(4-trifluoromethyl-phenyl)-ethyl]-biguanide, they also form, as novel substances, part of the subject-matter of the present application.
The substituted biguanides of the general formula (II) are obtained when substituted phenylalkylamines of the general formula (VII), 
in which
R3 and X are each as defined above
and/or acid adducts of compounds of the general formula (VII), such as, for example, the hydrochlorides
are reacted with cyanoguanidines of the general formula (IX) 
xe2x80x83in which
R1 and R2 are each as defined above,
if appropriate in the presence of a reaction auxiliary, such as, for example, hydrogen chloride, and if appropriate in the presence of a diluent, such as, for example, n-decane or 1,2-dichloro-benzene, at temperatures between 100xc2x0 C. and 200xc2x0 C. (cf. U.S. Pat. No. 3,860,648, Preparation Examples).
The substituted phenylalkylamines of the formula (VII) required as precursors for this purpose are known and/or can be prepared by processes known per se (cf. DE 2442845; DE 4038356; EP 490175, U.S. Pat. No. 5,300,437; J. Am. Chem. Soc. 105 (1983), 1578-1584; Tetrahedron: Asymmetry 4 (1993), 2093-2100; Biotechnol. Tech. 10 (1996), 335-338 xe2x80x94cited in Chem. Abstracts 125: 58008).
The cyanoguanidines of the formula (IX) are known chemicals for synthesis.
The formula (III) provides a general definition of the alkoxycarbonyl compounds further to be used as starting materials in the process (a) according to the invention for preparing compounds of the formula (I). In the formula (III), Z preferably or in particular has that meaning which has already been mentioned above,. in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for Z; Rxe2x80x2 preferably represents alkyl having 1 to 4 carbon atoms, and in particular represents methyl or ethyl.
The starting materials of the formula (III) are known chemicals for synthesis.
The formula (IV) provides a general definition of the substituted aminotriazines to be used as starting materials in the process (b) according to the invention for preparing compounds of the formula (I). In the formula (IV), R3, X and Z each preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (I according to the invention, as being preferred or as being particularly preferred for R3, X and Z; X1 preferably represents fluorine, chlorine, bromine or C1-C4-alkoxy, and in particular represents fluorine, chlorine, methoxy or ethoxy.
The starting materials of the general formula (IV) are known and/or can be prepared by processes known per se (cf. EP 300313).
The formula (V) provides a general definition of the nitrogen compounds further to be used as starting materials in the process (b) according to the invention for preparing compounds of the formula (I). In the formula (V), R1 and R2 each preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R1 and R2.
The starting materials of the general formula (V) are known chemicals for synthesis.
The formula (VI) provides a general definition of the substituted aminotriazines to be used as starting materials in the process (c) according to the invention for preparing compounds of the formula (I). In the formula (VI), R1, R2 and Z preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R1, R2 and Z; X2 preferably represents fluorine, chlorine, bromine or C1-C4-alkoxy, and in particular represents fluorine, chlorine, methoxy or ethoxy.
The starting materials of the general formula (VI) are known and/or can be prepared by processes known per se (cf. WO 95/11237).
The formula (VII) provides a general definition of the amino compounds further to be used as starting materials in the process (c) according to the invention. In the formula (VII), R3 and X each preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (IV) according to the invention, as being preferred or as being particularly preferred for R3 and X.
The starting materials of the general formula (VII) are known and/or can be prepared by processes known per se (cf. DE 2442845; DE 4038356; EP 490175; U.S. Pat. No. 5,300,437; J. Am. Chem. Soc. 105 (1983), 1578-1584; Tetrahedron: Asymmetry 4 (1993), 2095-2100; Biotechnol. Tech. 10 (1996), 335-338 xe2x80x94cited in Chem. Abstracts 125: 58008).
The formula (Ia) provides a general definition of the 2,4-diamino-1,3,5-triazines to be used as starting materials in the process (d) according to the invention for preparing compounds of the formula (I. In the formula (Ia), R1, R3, X and Z each preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R1, R3, X and Z.
As novel compounds, the starting materials of the general formula (Ia) also form part of the subject-matter of the present application; they can be prepared by the processes (a), (b) or (c) according to the invention.
The formula (VIII) provides a general definition of the alkylating, acylating or sulphonylating agents further to be used as starting materials in the process (d) according to the invention for preparing compounds of the formula (I). In the formula (VIII), R2 preferably or in particular has that meaning which has already been mentioned above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R2; Y preferably represents fluorine, chlorine, bromine, iodine, methoxy, ethoxy, methoxysulphonyloxy, ethoxysulphonyloxy, acetyloxy or propionyloxy.
The starting materials of the general formula (VIII) are known chemicals for synthesis.
If appropriate, the processes according to the invention for preparing the compounds of the formula (I) are carried out using a reaction auxiliary. Suitable reaction auxiliaries for the processes (a), (b), (c) and (d) are the customary inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, such as, for example, sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide or potassium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide; firthermore also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylmine, N,N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N,N-dimethylaniline, N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-ethyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-di-azabicyclo[2,2,2]-octane (DABCO), 1,5-diazabicyclo[4,3,0]-non-5-ene (DBN), or 1,8-diazabicyclo[5,4,0]-undec-7-ene (DBU).
Suitable diluents for carrying out the processes (a), (b), (c) and (d) according to the invention are, if appropriate, inert organic solvents. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; ketones, such as methyl isopropyl ketone or methyl isobutyl ketone; nitriles, such as acetonitrile, propionitrile or butyronitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-form-anilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; esters, such as methyl acetate, ethyl acetate, n- or -i- propyl acetate, n-, i- or s-butyl acetate; sulphoxides, such as dimethyl sulphoxide; alcohols, such as methanol, ethanol, n- or i-propanol, n- i-, s- or t-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, mixtures thereof with water or pure water.
In the practice of the processes (a), (b), (c) and (d) according to the invention, the reaction temperatures can be varied over a relatively wide range. Generally, the reaction is carried out at temperatures between 0xc2x0 C. and 300xc2x0 C., preferably between 10xc2x0 C. and 250xc2x0 C.
The processes (a), (b), (c) and (d) according to the invention are generally carried out at atmospheric pressure. However, it is also possible to carry out the processes according to the invention under elevated or reduced pressurexe2x80x94generally between 0.1 bar and 10 bar.
In the practice of the processes according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to use a relatively large excess of one of the components. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary, and the reaction mixture is generally stirred for several hours at the temperature required. Work-up is carried out by conventional methods (cf. the Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weed-killers. By weeds in the broadest sense, there are to be understood all plants which grow in locations where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera and Phalaris.
Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and railway tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for controlling weeds in perennial cultures, for example forests, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, on lawns, turf and pasture land, and for the selective control of weeds in annual cultures.
The compounds of the formula (I) according to the invention are suitable in particular for selectively controlling monocotyledonous and dicotyledonous weeds in monocotyledonous and dikotyledonous crops, both pre-emergence and post-emergence.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersing agents and/or foam-forming agents.
If the extender used is water, it is also possible to employ for example organic solvents as auxiliary solvents. Essentially, suitable liquid solvents are: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam-forming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and also protein hydrolysates; suitable dispersing agents are: for example lignin-sulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other possible additives are mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example
acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, asulam, atrazine, azimsulfuron, benazolin, benfuresate, bensulfuron(-methyl), bentazon, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bromobutide, bromofenoxim, bromoxynil, butachlor, butylate, cafenstrole, carbetamide, chlomethoxyfen, chloramben, chloridazon, chlorimuron(-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clopyralid, clopyrasulfuron, cloransulam(-methyl), cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, EPTC, esprocarb, ethalfluralin, ethametsulfiron(-methyl), ethofumesate, ethoxyfen, etobenzanid, fenoxaprop-ethyl, flamprop(-isopropyl), flamprop(-isopropyl-L), flamprop(-methyl), flazasulfuron, fluazifop(-butyl), flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurenol, fluridone, fluroxypyr, flurprimidol, flurtamone, fomesafen, glufosinate(-ammonium), glyphosate(-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl), hexazinone, imazamethabenz(-methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulftiron, norflurazon orbencarb, oryzalin, oxadiazon, oxyfluorfen, paraquat, pendimethalin, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachlor, propanil, propaquizafop, propyzamide, prosulfocarb, prosulfuron, pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyributicarb, pyridate, pyrithiobac(-sodium) quinchlorac, quinmerac, quizalofop(-ethyl), quizalofop(-p-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, tebutam, tebuthiuron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulfuron.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.
The active compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.